CN102140172A - Biomass material having multi isocyanate groups and forming method thereof - Google Patents
Biomass material having multi isocyanate groups and forming method thereof Download PDFInfo
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- CN102140172A CN102140172A CN2010101104546A CN201010110454A CN102140172A CN 102140172 A CN102140172 A CN 102140172A CN 2010101104546 A CN2010101104546 A CN 2010101104546A CN 201010110454 A CN201010110454 A CN 201010110454A CN 102140172 A CN102140172 A CN 102140172A
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- polyisocyanate
- living material
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- foam
- diisocyanate
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Abstract
The invention provides a method for forming a biomass material having multi isocyanate groups. The method comprises the following steps of: preparing a diisocyanate solution; and dissolving the biomass material having a plurality of hydroxyls, adding the diisocyanate solution and reacting the hydroxyls of the biomass material to form isocyanate groups. The invention also provides the biomass material having the multi isocyanate groups, formed by adopting the method. Through modification, the problem of non-uniform reaction of the hydroxyls on aryl and alkyl of the biomass material is solved. The modified biomass material can be applied to formulas of foam, coatings and PU (Polyurethane) resins.
Description
Technical field
The present invention relates to polyisocyanate-based living material, relates more specifically to its formation method and application.
Background technology
Polyurethane (polyurethane is hereinafter to be referred as PU) foam is the important people's livelihood or Industrial materials, is widely used in transportation, sports equipment, furniture, packing, fabric, and industry such as lagging material.The PU foam annual production on ground such as North America, Europe, Japan is greater than 2,300,000 tons, and the annual rate of growth in the whole world is 2-3%.Nearly 100,000 tons of Taiwan foam factory annual output, dog-eat-dog are needed new technology badly and are made the upgrading of foam quality, and exploitation high additive value product.
With PU industrial development and epoch transition, modern foam product developed multiple technologies as select new whipping agent for use, develop anti-yellow/stabilization aid, force the foaming cooling technology, varying pressure in foaming technology, carbon-dioxide system, and two isocyanic acid isophorones (isophorone diisocyanate is hereinafter to be referred as IPDI) be PU foam material and processing procedure.Present research center of gravity more is tending towards environmental protectionization (selecting for use of Halogen material), non-xanthochromiaization and high-qualityization.
Vulcabond is as two isocyanic acid isophorones (IPDI) or hexamethylene diisocyanate (hexamethylene diisocyanate, hereinafter to be referred as HDI) structure that is do not contain aromatic nucleus, be difficult for producing degradation phenomenas such as xanthochromia, begun to be applied to the dress material that foams, as underwear, medical device, transportation equipment, sports equipment, and field such as cushioning material, the global output value is about 30 to 3,500,000,000 yuan of New Taiwan Currencies.
Commercially available foam prepolymer is the thread-like molecule of difunctionality base at present, and itself can't form the three-D three-dimensional arrangement, and needs to add linking agent in addition to reach the crosslinked hardening effect of three-D.In addition in order to meet the environmental protection demand, various countries formulate rules more and encourage manufacturer will give birth to material to be applied in the various petroleum chemicals at present.With the xylogen is example, and its structure has great amount of hydroxy group, can be used as the prepolymer in the foam prescription.Yet the reactivity that is positioned at the hydroxyl on the alkyl in the xylogen is far below the hydroxyl that is positioned on the phenyl ring, and the uneven result of reaction will significantly reduce the product rerum natura.Therefore how to make the reactive unanimity of the hydroxyl of different the position of substitution in the xylogen, need the problem that overcomes for this area badly.
Summary of the invention
The object of the present invention is to provide a kind of method of the reactive consistent polyisocyanate-based living material of formation of the hydroxyl that can make different the position of substitution, and the polyisocyanate-based living material that forms of this method.
The invention provides the method for a kind of polyisocyanate-based living material of formation (biomass material havingmulti isocyanate groups), comprise preparation vulcabond solution; And after will having the living material dissolving of a plurality of hydroxyls, add in the vulcabond solution, make the hydroxyl reaction of living material form isocyanate group; Wherein vulcabond comprises aliphatic diisocyanate, aromatic diisocyanate or above-mentioned combination.
The present invention also provides a kind of polyisocyanate-based living material, wherein each isocyanate group is to be formed by the hydroxyl and the di-isocyanate reaction of giving birth to material, and vulcabond comprises aliphatic diisocyanate, aromatic diisocyanate or above-mentioned combination.
Compared with prior art, the invention has the advantages that: because method of the present invention makes all hydroxyl reactions of living material form isocyanate group in advance, can effectively improve the active uneven problem of hydroxyl reaction of living material different positions (on aromatic base and the alkyl), at room temperature the short period of time can be finished foamable reaction.And because the living material of above-mentioned upgrading of the present invention itself has had a plurality of isocyanate group, so the foam prescription need not add linking agent and can form the three-D three-dimensional arrangement.Polyisocyanate-based living material of the present invention can be applicable in foam, coating and the PU resin formula.
Embodiment
The invention provides a kind of method that forms polyisocyanate-based living material.At first, preparation vulcabond solution, the living material solution that will have a plurality of hydroxyls again adds vulcabond solution, makes the hydroxyl reaction of this life material form the isocyanic ester based prepolymers.With modal living material xylogen is example, above-mentioned reaction as shown in Equation 1, above-mentioned vulcabond can be aliphatic diisocyanate or aromatic diisocyanate.
In formula 1, a monomeric xylogen (Ligin) contains different aliphatics and aromatic hydroxyl.Via the molecular weight identification collocation volumetry molecular weight of xylogen as can be known, several monomers and hydroxyl have been extrapolated simultaneously.Then determine the usage quantity of vulcabond with above-mentioned hydroxy number.Each hydroxyl of xylogen can react with the isocyanate group of a side in the vulcabond, forms isocyanate group as shown in Equation 2.
Must it should be noted that at this hydroxyl of xylogen has different speed of reaction.For instance, the speed of reaction that is positioned at the hydroxyl on the aliphatic chain is than the speed of reaction of the hydroxyl on the phenyl ring fast about 5 times.Form isocyanate group for all hydroxyls all can be reacted, need to add the above isocyanate group of twice hydroxyl.
Being suitable for as vulcabond of the present invention is aliphatic isocyanates, comprise two isocyanic acid isophorones (IPDI), hexamethylene diisocyanate (HDI), methylene two (4-cyclohexyl isocyanate), cyclohexyl-methane two isocyanic acids (4,4 '-dicyclohexylmethane diisocyante, hereinafter to be referred as H
12Aliphatic diisocyanate or aromatic diisocyanate or above-mentioned combination such as MDI).In an embodiment of the present invention, the mol ratio of the hydroxyl of the isocyanate group of vulcabond and xylogen is between 2: 1 to 2.6: 1.If the consumption of vulcabond is very few, then can't make all hydroxyl reactions of xylogen form isocyanate group.If the consumption of vulcabond is excessive, then unreacted vulcabond will residue in the product, gives birth to the rigid characteristic reduction that material is had.
It should be noted that aforesaid method is not limited to modified lignin resin, also can be applicable to other living material that contains the active hydroxyl of two or more differential responses such as Mierocrystalline cellulose, hemicellulose or starch.
Polyisocyanate-based living material of the present invention can be applicable to a foam, PU resin, reaches formulation for coating material.With the above-mentioned living material that contains a large amount of isocyanate group, tensio-active agent, whipping agent, dibasic alcohol, and the mixture of water carry out foamable reaction (blowing) and cross-linking polymerization, last foam foamed solidification is shaped to foam.Compare with known skill, because living material of the present invention makes all hydroxyl reactions form isocyanate group in advance, can effectively improve the active uneven problem of hydroxyl reaction of living material different positions, at room temperature the short period of time can be finished foamable reaction.In addition, the living material of above-mentioned upgrading itself has had a plurality of isocyanate group, so the foam prescription need not add linking agent and can form the three-D three-dimensional arrangement.
In an embodiment of the present invention, dibasic alcohol be one end to end two ends have the polymkeric substance of hydroxyl, between 500 to 3000 polyester (polyester), or polyalcohols (polyol) is as polyoxyethylene glycol (PEG), polypropylene glycol (PPG) or analogue as weight average molecular weight.Above-mentioned polyalcohols also can be referred to as polyethers (polyether) alcohol.
In an embodiment of the present invention, the weight ratio of prepolymer and water is preferable between 100: 0.1 to 100: 10.If the ratio of water is too high, foam will chap.If the ratio of water is low excessively, expansion ratio will be not enough.
The said mixture high-speed stirring is even,, mixture can be poured on mould or tinuous production such as the conveying belt after second through about 1-300.After foaming 0.1-10 minute, can curing molding be foam.Foamable reaction can be finished under room temperature to 200 ℃, and is preferable between 20-100 ℃, best between 20-50 ℃.After the foam that aforesaid method forms shone with UV, its progression of anti-the xanthochromia can reach 5 grades.
Compare with known skill, foam of the present invention, its foamed time (blowing time) only need 1-300 second, be preferably 5-100 second, be more preferred from 10-50 second, the crosslinking polymerization time (gelling time) only needs 0.1-10 minute, be preferably 0.5-5 minute, be more preferred from 0.5-2 minute; And crosslinking reaction does not need heat, can react between the room temperature to 200 ℃ yet, and is preferable between 20-100 ℃, bestly finishes under 20-50 ℃.Because the reactive behavior height of prepolymer of the present invention can be simplified processing procedure.
Polyisocyanate-based living material of the present invention also can be applicable to a non-foaminess material prescription.Form the foam except carrying out foamable reaction, the living material that contains a plurality of isocyanate group of the present invention also can directly carry out crosslinking reaction with dibasic alcohol, to form non-foaminess product such as film.
For above and other objects of the present invention, feature and advantage can be become apparent, several embodiment cited below particularly are described in detail below:
Embodiment 1
The xylogen (available from the LS-103 of Borregaard LignoTech) that the present invention gets 200g is dissolved among the Polyol 1000 (Bayer company) of 100ml, forms lignin liquor, and gets the HDI (available from the Desmodur H of Bayer company) of 100g.Then, reacted again after dripping off 6 hours, confirm that with the NCO volumetry all hydroxyls of xylogen all react the formation isocyanate group stirring reaction in the vulcabond of 100 ℃ of lignin liquor addings.
Get the xylogen of the above-mentioned upgrading of 160g, the dibasic alcohol of 40g (available from the PPG-400 of Bayer company), the pentane (whipping agent) of 2g, the L580 (tensio-active agent of 1g, U.S. Union Carbide company product), reach 2g water thorough mixing after 20 seconds, pour the open space mould into, cross-linking polymerization foams, promptly get the foam finished product after 1 minute, this foam finished product has excellent mechanical intensity, and hardness is 70, modulus of compression is 90kgf/cm
2, bubble density is that 50 holes/English inch, the progression of anti-the xanthochromia are 5 grades, density is 0.3g/cm
3
Comparative example 1
Get the dibasic alcohol (available from the PPG-400 of Bayer company), the pentane (whipping agent) of 2g, the L580 (tensio-active agent of 1g of Polyol 1000,40g of HDI (available from the Desmodur H of Bayer company), the 40ml of 80g xylogen (available from the LS-103 of Borregaard LignoTech), 40g, U.S. UnionCarbide company product), reach 2g water thorough mixing after 20 seconds, pour the open space mould into, cross-linking polymerization directly foams, promptly get the foam finished product after 1 minute, the hardness of this foam finished product is 55, modulus of compression is 75kgf/cm
2, bubble density is that 30 holes/English inch, the progression of anti-the xanthochromia are 5 grades, density is 0.3g/cm
3Compare with embodiment 1,, therefore react inequality and abscess is thicker because the xylogen of comparative example 1 promptly carries out foamable reaction without upgrading.
Though the present invention discloses as above with several preferred embodiments; right its is not in order to limit the present invention; anyly be familiar with this skill person; without departing from the spirit and scope of the present invention; when can changing arbitrarily and retouching, so protection scope of the present invention is as the criterion when looking the scope that the accompanying Claim book defined.
Claims (9)
1. method that forms polyisocyanate-based living material comprises:
Prepare a vulcabond solution; And
After having the living material dissolving of a plurality of hydroxyls with one, add this vulcabond solution, make the hydroxyl reaction formation isocyanate group of this lifes material;
Wherein this vulcabond is aliphatic diisocyanate, aromatic diisocyanate or above-mentioned combination.
2. the method for the polyisocyanate-based living material of formation as claimed in claim 1, wherein this aliphatic diisocyanate is two isocyanic acid isophorones, hexamethylene diisocyanate, methylene two (4-cyclohexyl isocyanate), cyclohexyl-methane two isocyanic acids or above-mentioned combination.
3. the method for the polyisocyanate-based living material of formation as claimed in claim 1, wherein this living material with a plurality of hydroxyls is xylogen, Mierocrystalline cellulose, hemicellulose or starch.
4. polyisocyanate-based living material, wherein isocyanate group is to be formed by the hydroxyl and the di-isocyanate reaction of giving birth to material, and this vulcabond is aliphatic diisocyanate, aromatic diisocyanate or above-mentioned combination.
5. polyisocyanate-based living material as claimed in claim 4, wherein this living material with a plurality of hydroxyls is xylogen, Mierocrystalline cellulose, hemicellulose or starch.
6. be polyisocyanate-based living material as described in claim 4, wherein this aliphatic diisocyanate is two isocyanic acid isophorones, hexamethylene diisocyanate, methylene two (4-cyclohexyl isocyanate), cyclohexyl-methane two isocyanic acids or above-mentioned combination.
7. polyisocyanate-based living material as claimed in claim 4 is to be applied to a foam, PU resin, and formulation for coating material.
8. polyisocyanate-based living material as claimed in claim 7, wherein this foam prescription also comprises tensio-active agent, whipping agent, dibasic alcohol, reaches water.
9. polyisocyanate-based living material as claimed in claim 4 is to be applied to a non-foaminess material prescription.
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| CN2010101104546A CN102140172A (en) | 2010-02-03 | 2010-02-03 | Biomass material having multi isocyanate groups and forming method thereof |
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| CN2010101104546A CN102140172A (en) | 2010-02-03 | 2010-02-03 | Biomass material having multi isocyanate groups and forming method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601985A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Lignin melamine-based surface hydrophobic foam and preparation method thereof |
| CN105637036A (en) * | 2013-08-13 | 2016-06-01 | 能源实验室2000有限公司 | Process for the preparation of lignin based polyurethane products |
| CN107099017A (en) * | 2017-05-09 | 2017-08-29 | 东莞市普力达光学材料科技有限公司 | High density polyurethane foam and preparation method thereof and foam tape |
| CN109354717A (en) * | 2018-09-05 | 2019-02-19 | 安徽新翔包装材料有限公司 | A kind of degradable food pack |
| CN110983860A (en) * | 2019-12-24 | 2020-04-10 | 齐鲁工业大学 | Paper-based material surface coating agent, packaging paper and preparation method |
-
2010
- 2010-02-03 CN CN2010101104546A patent/CN102140172A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105637036A (en) * | 2013-08-13 | 2016-06-01 | 能源实验室2000有限公司 | Process for the preparation of lignin based polyurethane products |
| CN105637036B (en) * | 2013-08-13 | 2018-10-09 | 能源实验室 2000 有限公司 | The manufacturing method of sill quality polyurethane products |
| CN105601985A (en) * | 2016-03-27 | 2016-05-25 | 华南理工大学 | Lignin melamine-based surface hydrophobic foam and preparation method thereof |
| CN105601985B (en) * | 2016-03-27 | 2019-06-18 | 华南理工大学 | A kind of lignin melamine primary surface hydrophobic foam and preparation method thereof |
| CN107099017A (en) * | 2017-05-09 | 2017-08-29 | 东莞市普力达光学材料科技有限公司 | High density polyurethane foam and preparation method thereof and foam tape |
| CN109354717A (en) * | 2018-09-05 | 2019-02-19 | 安徽新翔包装材料有限公司 | A kind of degradable food pack |
| CN110983860A (en) * | 2019-12-24 | 2020-04-10 | 齐鲁工业大学 | Paper-based material surface coating agent, packaging paper and preparation method |
| CN110983860B (en) * | 2019-12-24 | 2022-06-07 | 齐鲁工业大学 | Paper-based material surface coating agent, packaging paper and preparation method |
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Application publication date: 20110803 |